title: Radical-transfer hydroamination of olefins with N-aminated dihydropyridines.
abstract: An efficient synthesis of N-phthalimidyl, benzamidyl, acetamidyl, carbamoyl, and ureayl derivatives of dihydropyridines and the application of these reagents as precursors for N-centered radicals are presented. These aminated dihydropyridines could be used in radical-transfer hydroamination reactions of various electron-rich as well as nonactivated olefins in the presence of thiols as polarity-reversal catalysts. These reactions worked without the aid of any transition metal. Steric and electronic effects exerted by the N-substituents of the N-centered radicals are discussed. In contrast to most metal-catalyzed processes, the radical hydroamination delivered the opposite regioisomer with excellent anti-Markovnikov selectivity. Hydroamination products were obtained as protected amines that are readily isolated.
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.
authors.forename: Chih-Ming
authors.initials: CM
authors.lastname: Chou
authors.forename: Joyram
authors.initials: J
authors.lastname: Guin
authors.forename: Christian
authors.initials: C
authors.lastname: Mück-Lichtenfeld
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.forename: Armido
authors.initials: A
authors.lastname: Studer